We present a systematic investigation of molecule-metal interactions for transition-metal phthalocyanines (TMPc, with TM = Fe, Co, Ni, Cu) adsorbed on Ag(100). Scanning tunneling spectroscopy and density functional theory provide insight into the cha
rge transfer and hybridization mechanisms of TMPc as a function of increasing occupancy of the 3d metal states. We show that all four TMPc receive approximately one electron from the substrate. Charge transfer occurs from the substrate to the molecules, inducing a charge reorganization in FePc and CoPc, while adding one electron to ligand pi-orbitals in NiPc and CuPc. This has opposite consequences on the molecular magnetic moment: in FePc and CoPc the interaction with the substrate tends to reduce the TM spin, whereas in NiPc and CuPc an additional spin is induced on the aromatic Pc ligand, leaving the TM spin unperturbed. In CuPc, the presence of both TM and ligand spins leads to a triplet ground state arising from intramolecular exchange coupling between d and pi electrons. In FePc and CoPc the magnetic moment of C and N atoms is antiparallel to that of the TM. The different character and symmetry of the frontier orbitals in the TMPc series leads to varying degrees of hybridization and correlation effects, ranging from the mixed-valence (FePc, CoPc) to the Kondo regime (NiPc, CuPc). Coherent coupling between Kondo and inelastic excitations induces finite-bias Kondo resonances involving vibrational transitions in both NiPc and CuPc and triplet-singlet transitions in CuPc.
We evaluate the electronic, geometric and energetic properties of quasi 1-D wires formed by dangling bonds on Si(100)-H (2 x 1). The calculations are performed with density functional theory (DFT). Infinite wires are found to be insulating and Peierl
s distorted, however finite wires develop localized electronic states that can be of great use for molecular-based devices. The ground state solution of finite wires does not correspond to a geometrical distortion but rather to an antiferromagnetic ordering. For the stability of wires, the presence of abundant H atoms in nearby Si atoms can be a problem. We have evaluated the energy barriers for intradimer and intrarow diffusion finding all of them about 1 eV or larger, even in the case where a H impurity is already sitting on the wire. These results are encouraging for using dangling-bond wires in future devices.
